Polymerization of aliphatic monomers in presence of aromatic-olefin copolymer and resulting product



United States Patent PULYMEREZATRQN ill ALHHATIC MUNQMERS IN PRESENCE 0F ARQMATlQ-OLEFW Cfllbfil if- MER AND RESULTENG PRQDUCT William H. myers, 229 Sylvania llaee, Westfield, Nil,

and David W. Young, 135% Clyde Ave, Hornew'ood, ill.

No ra ning. (Zontinuation oi application No. 309,370, Sept. 12, 1952, This application lune 3, 1059, Ser. No. 017,729

13 Claims. (til. 260 455) This invention relates to a novel polymerization process and resulting products thereof. More particularly it relates to the preparation of high molecular weight polymers by the mass polymerization or emulsion polymerization technique, in the presence of very high molecular Weight cyclic-aliphatic copolymers which have been made by polymerization at temperatures substantially below 0 C. in the presence of a Friede-l-Craft catalyst.

It has heretofore been suggested that certain high molecular weight polymers such as polystyrene, polymethylrnethacrylate, etc. which per se are too brittle for many purposes, can be plasticized and improved in flexibility by compounding therewith certain high molecular weight copolymers such as one made by copolymerizing isobutylene and styrene at temperatures below 0 C., in the presence of a Frieclel-Craft catalyst. However, the compounding of two such high molecular weight polymeric materials is attended with substantial difiiculty in mixing and often does not obtain a perfectly homogeneous composition. a

It has also been suggested that styrene could be polymerized in the presence of a high molecular weight polymer such as polyisobutylene, by first preparing the polybutene at a temperature below 0 (3., and then dissolving this polymer in monomeric styrene, together with a small amount of benzoyl peroxide catalyst and heating the mixture. This suggested procedure works satisfactorily for isobutylene polymers of only moderately high molecular weight, such as from about 1,000 to 10,000 or 15,000, but when this process is applied to a higher molecular weight polybutene such as one having a molecular weight of 50,000 or 100,000, the finished composition after polymerization of the styrene, shows a cloudiness and other undesirable characteristics due to the incompatibility of the high molecular weight polybutene with the high molecular weight polystyrene. Also, this composition cannot be sheeted into thin films.

Now, according to the present invention, it has been found that a number of unexpected advantages are obtained if styrene is polymerized in the presence of a high molecular weight copolymer of styrene and isobutylene having an intrinsic viscosity of at least 0.5 and a combined styrene content of about 50% to 80%, preferably about 60% to 70% by weight.

Although styrene-isobutylene copolymers having a lower intrinsic viscosity, such as from 0.1 to 0.4, are sufiiciently low in molecular weight to be compatible with the finished polystyrene, even when a wide range of styrene and isobutylene proportions are used in making the copolymer, nevertheless such low molecular weight and low in rinsic viscosity copolymers of styrene and isobutylene are not satisfactory for the purposes of the present invention, because they are either soft and sticky or soft and brittle, and are so low in tensile strength that they greatly impair the properties of the polystyrene produced in their presence, without imparting the desired plasticity and toughness in the finished composition.

It is also noted that styrene-isobutylene copolymers even having an intrinsic viscosity of at least 0.5, but having a combined styrene content considerably below 50% by weight, such as to 40% by weight, are not puz- 'ice

6d sufficiently compatible with high molecular weight polystyrene produced in its presence to permit satisfactory use according to the process of the present invention. On the other hand, a high molecular weight copolymer of styrene and isobutylene having an intrinsic viscosity as high as 0.5 but having a combined styrene content much higher than such as in the range of to is compatible with polystyrene produced in its presence, but is too brittle to make any substantial reduction in the inherent brittleness of the polystyrene itself.

According to the present invention, in place of the styrene-isobutylene copolymers mentioned above, one may also use other cyclic-aliphatic copolymers having a similarly high intrinsic viscosity of at least 0.5, preferably 0.7, and having a content of combined cyclic constituent sufiiciently high that the copolymer will be compatible with polystyrene or other heat-polymerized polymers produced in its presence, and yet below the amount of combined cyclic constituent which impart brittleness to the copolymer and prevents it from plasticizing and ilexibilizing the polymers made in their presence. *For instance, instead of styrene in such copolymers, one may use alpha methyl styrene, paramethyl styrene, alphamethyl paramethyl styrene, 2,4-dichlorostyrene, parachlorostyrene, :alpha-methoxy styrene, Z-chloroparamethyl styrene, andother polymerizable mono-olefinic aromatic compounds, such as vinyl naphthalene, dihydronaphthalene, indene, etc. In place of isobutylene in the copolymer one may use other lower aliphatic olefi-ns having from 2 to 8 carbon atoms, preferably, 3 to 5 carbon atoms such as methyl- 2, butene-l, propylene, iso-octene, and even ethylene under certain cir-ctunstances, as will be noted later.

Although, it is preferred for most purposes that the above described cyclic-aliphatic linear type copolymer be substantially saturated as will naturally result from the use of the two types of reactants described above, it may be desirable under some circumstances to make a product having a slight unsaturation, such as having an iodine number less than 10 and preferably about 0.1 to 1. Such a result may be obtained by using a third copolymerization reactant namely a small amount of a diolefin or other polymerizable polyene, as for instance about 0.5% to 3% of isoprene, or about 1% to 10% or so of butadiene. Other polyenes which may be used include divinylbenzene, Z-methylpentadiene, cyclopentacliene, myrcene, allo-ocimene, 2-3 dimethyl butadiene l-3, etc. When three reactants are used as thus suggested, the resulting copolymer may be referred to as a tripolymer.

In carrying out the copolymerization of the styrene and isobutylene, or other reactants mentioned above, in order to make a high molecular weight linear type copolyrner having an intrinsic viscosity of at least 0.5, it is preferred to use a fairly strong Friedel-Craft catalyst at a temperature below 50 C. and preferably below -80 C., and this should preferably be done in the presence of a lower alkyl halide of less than 4 carbon atoms, such as methylchloride or ethylchloride, as solvent for the copolymerization reactants and resulting copolymer. Re-

frigeration may be effected by known methods such as by' internal or external cooling coils or jacket, or by internal refrigeration by the evaporization of a very low boiling liquefied gaseous material such as propane, ethane, ethylene, or even methane, and the like, using the latent heat of evaporation of the refrigerant to absorb the heat of polymerization, as well as to cool the initial reactants down to the desired copolymerization temperature before actually starting the copolymerization. i

The catalyst is prepared by dissolving aluminum chlo ride, titanium tetrachloride or boron fluoride or other suitable Friedel-Craft catalyst or complex in a lower ing emulsion. emulsion technique, the amount of water or other aqueous alkyl halide solvent such as ethyl chloride at room temperature or slightly above, or in methyl chloride at its boiling point which is about 23 C., and then cooling the resultant catalyst-solvent solution down to the desired copolyrnerization temperature.

The copolymerization reaction is fast and vigorous, and as soon as it is completed, residual catalyst is inactivated by addition of a small amount of lower alcohol such as isopropyl alcohol or ethyl alcohol, or other suitable hydrolyzing agents such as aqueous caustic soda or water, etc. 'In some cases, the desired high molecular weight .copolymer is thrown out of solution during the step of hydrolyzing residual catalysts, and in such case may be separated from the liquid layers and in some cases the copolymer remains in solution in the lower alkyl halide solvent while the hydrolized catalyst forms an aqueous or alcoholic sludge layer which may be separated, .and then the copolymer may be recovered from the solvent solution either by evaporation or by precipitation with a larger amount of alcohol or acetone and the like. It is preferable to wash the high molecular weight copolymer .one or more times with Water, alcohol, dilute aqueous caustic soda solution or other suitable media and then to dry it, preferably by heating and milling in order to pressure of 200 to 2,000 atmospheres with a peroxide or oxygen catalyst. These copolymers may be used alone or preferably together with a low temperature Frie'del-Craft .copolymer, e.g. styrene-isobutylene copolymer for dissolving in styrene and heat-polymerizing.

According to the present invention, the high molecular weight copolymer thus prepared, having a Staudinger molecular weight of at least about 20,000 and an intrinsic viscosity (in toluene) of at least 0.5, is now dissolved in a concentration of about to 50% preferably about to 30% by weight in styrene or other suitable heatpolymerizable monomer, together with a small amount of polymerization catalyst such as benzoyl peroxide, etc., and then the resultant solution is heated either directly as such according to the so-called mass polymerization technique, or by first emulsifying this copolymer-monomer solution with water or other aqueous medium by means of a suitable emulsifying agent such as soaps, e.g. sodium stearate, etc., and then finally heating the result- When operating according to this latter medium or even some organic medium insoluble in the polymerizable monomer should be about 20 to 200% by weight based on the polymerizable monomer used, and the emulsifying agent should generally be used in the concentration of about 0.5 to 5% by weight based on the amount of Water used.

The temperature at which such heat polymerization, should normally be carried out will range from about room temperature, or about 20 C., up to about 125 C., and preferably from about 30 to 80 C. The time required for this heat polymerization, varies inversely according to the temperature used, ranging from about 2 to 12 hours at 80 C., to about 6 to 120 hours at 40 C., up to about 180 to 1000 hours at 20 C., and the temperature-time conditions required vary somewhat with difierent heat-polymerizable monomers.

Although it is not certain, it is believed that in addition to obtaining a truly homogeneous composition of styreneisobutylene copolymer and polystyrene, some of the styrene monomer actually heat-polymerizes onto the styrene-isobutylene copolymer molecules present, to form 'a new type of composite molecule, e.g. a di-polymeric molecule or generically a poly-polymeric molecule, as it may contain even three or more polymers built up together one after the other.

"of styrene-isobutylene copolymer Instead of using styrene as the polymerizable monomer, other materials may be used such as paramethyl styrene, parachlor styrene, 2-chlorparamethy1 styrene, 2-4-dichlor styrene, 2-5-dichlor styrene, etc., parabrom styrene, 3- methoxy styrene, 4-methoxy styrene, 4-phenoxy styrene, or other heat-polymerizable substituted styrcnes or corresponding other hydrocarbons such as indene, vinylnaphthalene, dihydronaphthalene, etc.

Instead of using the above mentioned aromatic types of heat-p-olymerizable monomers, the invention is applicable to other types of heat polymerizable monomers, e.g. mono-olefinic unsaturated alcohols, ethers, esters, acids, and hydrocarbon halides, such as vinylchloride, vinylacetate, vinylidene chloride, methylmethacrylate,

'lauryl methacrylate or various other unsaturated esters such as fumarates, etc., as well as acrylonitrile, diolefins such as butadiene, isoprene, etc. or mixtures thereof. In the case of these various polymerizable unsaturated aliphatic compounds, the high molecular weight cyclicaliphatic copolymer to be dissolved in the heat polymerizable monomer, preferably should have a lower content of combined cyclic constituent than discussed above for use in the presence of heat-polymerizable styrene or other aromatic materials. For instance, when heat polymerizing methylmethacrylate, laurylmethacrylate or a mixture of vinyl chloride and vinyl acetate, one may use a styrene-isobutylene copolymer or a chlorstyrene-isobutylene copolymer containing about 10 to 60%, preferably about 20 to 50% by Weight of combined cyclic constituent.

Having thus described the general principles of the invention some experimental data are given for the sake of illustration and to show some of the unexpected advantages of the invention.

EXAMPLE 1 A styrene-isobutylene copolymer was prepared at 103 C. to produce a copolymer having an intrinsic viscosity (in toluene) of 0.84, and having about 60% by Weight of combined styrene. Then 10% by weight of this copolymer was dissolved in pure monomeric styrene. 2000 ml. of the resulting solution was treated with 0.2% of benzoyl peroxide at room temperature and the solution heated under reflux at 40 C. for 8 hours, at the end of which time the materials were heated to approximately 150 C. for about 10 minutes to soften it sufiiciently so that it would flow out of the reactor onto a piece of holland cloth to cool. This polymeric product which was made in situ in the presence of 10% by weight was examined and found to have good clarity and was tested for various physical properties in comparison with a plain polystyrene made under the same polymerization conditions except in the absence of the styrene isobutylene copolyrner, and also in comparison with a mill-mixed blend of 10% of the Property, 110W made Mill-mixed in situ Heat softening point C.) (modified Wllhams plasticity) 105 92 95 Distortion temp. O.) 80 76 75 Brinell hardness 2O 18 18 Rockwell hardness (M Number) 75 68 70 Compression strength (lbs/sq. in.) 15, 000 13, 500 13,000 Tensile 5, 000 3, 000 3, 800 Impact strength, ft. lbs/1n of notch Charpy Sunpl beam 3.100 4, 000 5, 000 Flcxure strength, lbs/sq. in. 3, 800 2, 3, 000 Clarit Clear Cloudy Crescent tear, lbs/linear inch 21 188 1 Very slightly cloudy.

The above data shows the polymerization of the styrene in situ in the presence of the high molecular weight styrene-isobutylene copolymer effected a very substantial modification of the inherent brittleness and refractoriness of the plain polystyrene. The reduced brittleness is particularly shown by a reduction in the Brinell hardness from 20 to 18 and by the superior impact strength and tear resistance. It is also remarkable that the desired amelioration of some of the undesirable characteristics of plain polystyrene can be etfected with such a relatively slight loss in some of the strength characteristics. For instance, whereas the plain polystyrene had a flexure strength of 3,800 lbs/sq. in. the modified polystyrene had a flexure strength of 3,000 lbs/sq. in., which is unexpectedly high considering that when by weight of a similar styrene-isobutylene copolymer was mixed on a hot mill with 90% by weight of an 80,000 molecular weight polystyrene, substantially the same as made in the above experiment, the resulting mixture, even after'lS minutes mixing on the hot mill, had a flexure strength of only 2,100 lbs/sq. in. This is believed due to inability to obtain a completely homogeneous mixture by the hot milling method. Also, the clarity as obtained in 5, 15, 20, and 30 minute milling tests with 10% by weight of a similar styrene-isobutylene copolymer in an 80,000 molecular weight polystyrene, proved that the degree of clarity of a inch pressed sheet was better for the samples that were made by dissolving the styrene-isobutylene copolymer in the styrene and then heat polymerizing the monomer rather than making both polymers first and then mixing them on the hot mill. Here again it is believed that the lesser clarity obtained with the mill mixing is due to lack of a completely homogeneous composition, whereas the polymerization of the styrene in the presence of the styrene-isobutylene copolymer gives a. completely homogeneous composition.

Improvement was noted in machineability, extrusion flow properties, and resistance to moisture vapor penetration with additions of up to 20% of this co-polymer in polystyrene. 10% of the copolymer reduces the M.V.P. (moisture vapor permeability) of polystyrene by 30% (by the General Foods method).

EXAMPLE 11 Another set of tests was made similar to those in Example I expect that in this case 30% by weight of the styrene-isob-utylene copolymer, was dissolved in the styrene monomer, and after addition of the benzoyl peroxide catalyst the resulting mixturre was heated for 12 hours. The slightly longer time of polymerization was required on account of the diluting effect of the larger amount of styrene-isob-utylene copolyrner used in this example as compared to Example I. The resulting 30% copolymer-modified polystyrene, and a corresponding sample of plain polystyrene made under the same conditions except in the absence of any styrene-isobutylene cop-olymer, were subjected to various physical tests with the following results.

The above data indicate, particularly in the Brinell hardness, that the modified polystyrene made in the presence of the 30% of the styrene-isobutylene copolymer,

was much softer and more workable than the plain polystyrene made under the same polymerization conditions except in the absence of the styrene-isobutylene copolymer. For instance, the reduction of the Brinell hardness from 20 to 12 shows the tremendous plasticizing eiiect of the styrene-isobutylene copolymer.

Here again, in Example II, as was the case in Example I, the modified polystyrene, i.e. made in the presence of the styrene-isobutylene copolymer, showed a much higher degree of clarity when pressed into a slab A inch thick, than did a mixture of 70% of plain polystyrene of 80,000 molecular weight and 30% of the same styrene-isobutylene copolymer when mixed on a hot mill. Samples made with various milling times of 5, 15, and 30 minutes, all showed poorer clarity than the sample made by polymerizing the styrene directly in the presence of the styrene-isobutylene copolymer. As noted above, the composition made according to the present invention by polymerizing the styrene in situ in the presence of the styrene-isobutylene cop olyrner, is a completely homogeneous mixture, whereas the hot mill mixing of two high molecular polymers apparently does not obtain an absolutely homogeneous mixture.

EXAMPLE III A styrene-isobutylene copolymer having about 50% by weight of combined styrene and having an intrinsic viscosity of 0.95, was dissolved in a concentration of about 5% by weight, in styrene containing peroxide catalyst, and the solution was heated to 60 C. for 25 hrs. The resulting composition indicated that the copolymer with 50% styrene was less compatible in the polystyrene than the copolymers that contained 60% styrene by analysis.

Copolymers having lower proportions of combined styrene, eg. 40%, 20%, etc., and having an intrinsic viscosity of at least 0.5, are not compatible with high molecular weight polystyrene made either in situ or mill-mixed.

EXAMPLE IV A styrene-isobutylene copolymer having a combined styrene content of about by weight and having an intrinsic viscosity of 0.63 was made at a copolymerization temperature of C. using a catalyst consisting of 0.5% of A101 in methyl chloride, and using 3 volumes of methyl chloride as solvent per volume of copolymerization reactants. The resulting copolymer is per se a hard resin, almost more resembling a polystyrene that it does a styrene-isobutylene copolymer having a combined styrene content of about 60%, as used in Example I. 20% by weight of this styrene-isobutylene copolymer of 80% styrene content and 0.63 intrinsic viscosity was dissolved in pure styrene monomer and, after the addition of 0.2% of benzoyl peroxide, the mixture was heated at 40 C. for 10 hours, at the end of which time it was heated to C. to soften it, and poured out onto holland cloth to cool. The modified polystyrene was then subjected to various physical tests in comparison with some plain polystyrene which had been polymerized under the same conditions except without the addition of any styreneisobutylene copolymer. The results of these physical tests were as follows:

Table 3 Present invention Percent polystyrene 100 Percent copolymer (80% styrene) 0 20 "Heat softening point C.) 112 100 Brinell hardness 21 1Q Rockwell hardness 75 70 The above data indicate that although the styrene-isobutylene copolyrner with 80% combined styrene does have some plasticizing efiect on the polystyrene, as indicated by a reduction of the Brinell hardness from 21 to 19, and the Rockwell hardness from 75 to 70, it required 20% of this particular copolymer to eiiect this plasticizing, whereas in Example I only 10% styrene-isobutylene copolymer, having a combined styrene content of 60%, \elfected a substantially equivalent amount of plasticizing, and therefore was practically twice as effective in plasticizing characteristics as the styrene-isobutylene copolymer of 80% combined styrene.

The composition prepared according 'to the present invention :as described in Example I namely made by heat-polymerizing styrene in situ in the presence of 10% by weight of high molecular weight styrene-isobutylene copolymer having 60% combined styrene and 40% isobutylene, which overall composition therefore contains about 4% by weight of isobutylene, is much more plastic and workable than a plain styrene-isobutyiene copolymer made with 96% styrene and 4% isobutylene. Similarly the composition made by polymerizing styrene in the presence of 30% by weight of styrene-isobutylene copolymer of 60% combined styrene, which composition therefore has about 12% of isobutylene on the basis of the overall composition, is surprisingly superior in plastic and workable characteristics to a styrene-isobutylene cpolymer made with 88% of styrene and 12% of isobutylene.

EXAMPLE V 20% by weight of styrene-isobutylene copolymer as used in Example I was dissolved in vinyl chloride and the latter was polymerized. The mixture was more plastic at room temperature than polyvinyl chloride plasticized with diphenyl, and had superior electrical properties and resistance to moisture vapor penetration.

As another feature of the invention it is contemplated that instead of using a. single styrene-isobutylene copolymer, one may use a mixture of several difierent copolymers I aving physical properties or other characteristics which supplement each other. For instance, one may advantageously dissolve by weight of a styreneisobutylene copolymer having 80% combined styrene and an intrinsic viscosity of 0.63 (as used in Example 4) along with 10% by weight of a styrene-isobutylene copolymer having a 40% combined styrene and an intrinsic viscosity of 0.8 or so, in 80% by weight of styrene monomer and then heat-polymerizing the mixture. One may also heat-polymerize styrene, etc. in the presence of two cyclic-aliphatic copolymers of which one is a high molecular Weight tough copolyrner having an intrinsic viscosity of at least 0.5 and a combined styrene content of 50 to 80% or so, and the other is a low molecular weight hard brittle copolymer having an intrinsic viscosity of about 0.1 to 0.4 and a similar combined styrene content of about 50 to 80%, preferably about 55 to 70%, by weight, e.g. a styrene-isobutylene copolymer of 60% combined styrene, made at 23 C. and having an intrinsic viscosity of 0.2.

Also, after the heat-polymerizable monomer has been heat-polymerized in the presence of the high molecular weight cyclic-aliphatic copolymer, the resulting composition may, if desired, with addition of pigments, other resins, wood flour, wax, clay, etc., be worked on a rubber mill etc., to form sheets, etc. Curing or other compounding agents may of course be added, and the resulting composition cured or vulcanized, if one or more of the polymers is curable.

Some additional data will now be given on application of the invention to aliphatic heat-polymerizable monomerspalone or with minor amounts of styrene or its homologues.

EXAMPLES VI AND VII A styrene-isobutylene copolymer of 60% styrene and intrinsic viscosity about 0.8 was solvated in pure styrene monomer, and then acrylonitrile was added to this solution. The amount of acrylonitrile added was 25% by 8 weight based 'on styrene acrylonitrile mixture. In other words, the ratio of styrene to acrylonitrile was 75 to 25 and the amount of copolymer present in the blend was varied from 0 to 10%. The mixtures were polymerized in 4 volumes of water to 1 volume of reactants. To the mixture were added 2% sodium oleate and A1 of potassium persulfate, emulsified and then heated with good agitation to 30-4-0" C. for 20 hours. The'total yield of dry polymer was well above 92% in each case.

Inspections on each polymer are listed in the following table:

Table 4 Percent styrene-nitrile mixture (75-25) 95 00 Percent styrene-butene resin 0 5 10 S. gr 1.03 0. 98 Tensile strength, lbs/sq. in 5, 590 5, 540 Flcxural strength, lbs/sq. in. (4

sample) 1, 950 900 Impactstrength, it.lb./periu. ofnotch, Izod- 1.0 1. 4 1. 8 Rockwell hardness (M scale) 93 82 65 Heat distortion, C 86 82 Dielectric constant, 1 kc... 0.007 0. 006 Water absorption 1% after days at RT O. 31 0. 28 Flammability, in. per min. Slow Slow Clarity Opaque 1 Transparent.

EXAMPLE VIII 10% by weight of a copolymer of 60% by wt. of pchloro styrene and 40% of isobutylene, having an intrinsic viscosity of 0.8, was solvated in vinyl chloride. The mixture was emulsified in H O (ratio of water to reactants was 4 to 1), and polymerized at 50-60 C. for 18 hours, using 2% Na oleate and 0.3% K persulfate. The yield of final polymer was 90.1%. The new mixture had improved processing properties on a hot rubber mill at 300 F. Inspections on the product are recorded as follows:

Tensile 5,930 lbs/sq. inch. Elongation percent 15.

Experiments proved that the U.V. light stability of the cosynthesis product, as made above was better than the pure polyvinyl chloride resin made without the use of the p-chloro styrene-isobutylene resin.

EXAMPLE IX 30% by weight of a styrene-isobutylene copolymer of 40% styrene content, and about 1.3 intrinsic viscosity, was solvated in butadiene. Styrene was then added until the ratio, on a wt. basis, of styrene to butadiene was 25% styrene and 75 butadiene. This mixture was then diluted with 4.4 volumes of H 0, emulsified and polymerized, at 60 C. with 4% Na oleate and 0.5% K persulfate catalyst. Time or" polymerization was 8 hours. Yield of polymer, on monomer basis, was 88.7%. Product was coagulated with NaCl, water-washed and dried. Milling tests proved that the synthetic rubber product could be calendered, and worked to form sheets that were thin (0.10") and flexible and smooth. Inspections on the product are listed Tensile; 104 0 lbs./sq. inch. Elongation, percent 390.

This example shows the improvement in processability and other characteristics effected by this invention.

Some other ways of applying the invention are outlined as follows:

of mono-olefinic unsaturated esters, mono-olefinic unsaturated hydrocarbon halides, and conjugated diolefins, and

Styrene-isobutylene copolymer Heat-polymerizable monomers Ex. No.

Kind Percent Amt, Percent Kind Polym. method styrene percent 50 1O 90 Vinyl chloride (95), vinyl acetate (5) Mass. 40 30 7O Butadiene Emulsified. 5O 1O 9O Butadiene (75), styrene (25). D0. 50 90 Methacrylonitrile D0, 50 10 90 Vinylidene chloride..--- Mass. 60 10 90 Methyl methacrylate Do. 50 10 90 Butadiene (74), acrylonitrile (26 Emnlsified. 50 10 90 Butadiene (75), styrene Sodium cat. XVII Like XVII...- Excep Mass (perox. cat.) no diluent. XIX... Like XVIII... .d0 2vol.petroleumnaphthaasdiluent.

This application is a continuation of application Scr. No. 309,378, filed September 12, 1952, now abandoned, which is a continuation-in-part of application Serial No. 713,810, tiled December 3, 1946, now Patent 2,610,962.

What is claimed is:

l. A process which comprises dissolving a copolymer of about 60% by weight of styrene, and about 40% of isobutylene, having an intrinsic viscosity above 0.5, in a concentration of about 5 to 50% by Weight in a heat-polymerizable monomer comprising at least 90% by weight of vinyl chloride, and heating the resultant mixture in the presence of a polymerization catalyst to a temperature of about 30 to 100 C. to make a homogeneous mixture of the styrene-isobutylene copolymer and the heat-polymerization product.

2. A homogeneous composition made by dissolving about 20% by weight of a high molecular weight co polymer of styrene and isobutylene having about 60% by weight of combined styrene and having an intrinsic viscosity above 0.5, in 80% by Weight of monomeric vinyl chloride, andheating the resulting mixture to polymerize said vinyl chloride to a high molecular Weight in situ in the presence of said styrene-isobutylene copolymer.

3. Process which comprises dissolving about 5 to 50% by weight of a copolymer of about 10-60% by weight of a polymerizable mono-olefinic aromatic compound selected from the group consisting of hydrocarbons and chlorostyrenes, and about 90-40% of a monoolefin of 2 to 8 carbon atoms, having an intrinsic viscosity above 0.5 and having an iodine number less than 10, in a heatpolymcrizable monomer comprising at least 74% by weight of a mono-olefinic aliphatic compound, and then heating the resultant mixture at about 20-125 C. to eifect polymerization of said heat-polymerizable monomer in situ in the presence of said aromatic-olefin copolymer.

4. Process which comprises dissolving about 5 to 50% by weight of a copolymer of about 10-60% by Weight of a polymerizable mono-olefinic aromatic compound selectcd from the group consisting of hydrocarbons and chlorostyrenes, and about 90-40% of a mono-olefin of 2 to 8 carbon atoms, having an intrinsic viscosity above 0.5 and having an iodine number less than 10, in a heatpolymerizable monomer comprising at least 90% of a mono-olefinic aliphatic hydrocarbon halide, and then heating the resultant mixture at about 20-125 C. to effect polymerization of said heat-polymerizable monomer in situ in the presence of said aromatic-olefin copolymer.

5. Process which comprises dissolving about 5 to 50% by Weight of a copolymer of about 10-60% by weight of a polymerizable mono-olefinic aromatic compound selected from the group consisting of hydrocarbons and chlorostyrenes, and about 90-40% of a mono-olefin of 2 to 8 carbon atoms, having an intrinsic viscosity above 0.5 and having an iodine number less than 10, in 50 to 95% by weight of a compatible heat polymerizable monomer comprising at least 74% by weight of an unsaturated aliphatic compound selected from the group consisting then heating the resultant mixture at about 20-l25 C.

to effect polymerization of said heat-polymerizable monomer in situ in the presence of said aromatic-olefin copolymer.

6. Process according to claim 5 in which the unsaturated aliphatic compound is a mono-olefin-ic unsaturated ester.

7. Product comprising a homogeneous mixture of a high molecular weight copolyrner comprising about 10-60% by weight of a polymerizable mono-olefinic aromatic compound selected from the group consisting of hydrocarbons and chlorostyrenes, and about -40% of a mono-olefin of 2 to 8 carbon atoms, said copolymer having an intrinsic viscosity above 0.5 and having an iodine number less than 10, having homogeneously admixed With said copolymer another high molecular weight polymerization product made by heating to polymerization temperature at least 5095% by weight of a heatpoiymer-izable monomer comprising at least 74% by wt. of an unsaturated aliphatic compound selected from the group consisting of mono-olefinic unsaturated esters, mono-olefinic unsaturated hydrocarbon halides, and conjugated diolefins, in situ in the presence of 5 to 50% by Weight of the first-mentioned copolymer.

8. Product according to claim 7 in which the copolymer is a styrene-isobutylene copolymer.

9. A process which comprises dissolving a copolymer of about 60% by weight of ohlorostyrene and about 40% of isobutylene, having an intrinsic viscosity above 0.5, in a concentration of about 5 to 50% by weight in a heatpolyme-rizable monomer comprising at least 90% by weight of vinyl chloride, and heating the resultant mixture in the presence of a polymerization catalyst to a temperature of about 30 to C. to make a homogeneous mixture of the styrene-isobutylene copolymer and the heat-polymerization product.

10. Process which comprises dissolving about 5 to 50% by weight of a copolymer of about =10-60% by weight of a polymerizable mono-oleiinic aromatic compound selected from the group consisting of hydrocarbons and chlorostyrenes, and about 90-40% of a mono-olefin of 2 to 8 carbon atoms, having an intrinsic viscosity above 0.5 and having an iodine number less than 10, in a heat-polymerizable monomer comprising at least 74% by weight of butadiene, and then heating the resultant mixture at about 20-125 C. to effect polymerization of said heat-polymerizable monomer in situ in the presence of said aromaticolefin copolymer.

11. Process which comprises dissolving about 5 to 5 0% by Weight of a copolymer of about 10-60% by weight of a polymerizable mouo-olefinic aromatic compound selected from the group consisting of hydrocarbons and chlorostyrenes, and about 90-40% of a mono-olefin of 2 to 8 carbon atoms, having an intrinsic viscosity above 0.5 and having an iodine number less than 10, in a heat-polymerizable monomer comprising at least 90% by weight of methacrylonitnile, and then heating the resulting mixture 1 1 at about 20-125 C. to effect polymerization of said heatpolymerizable monomer in situ in the presence of said aromatic-olefin copolymer.

12. Process which comprises dissolving about 5 to 50% by Weight of a copolymer of about 1 060% by Weight of a polymerizable mono olefinic aromatic compound selected from the group consisting of hydrocarbons and chlorostyrenes, and about 90-40% of a mono-olefin of 2 to 8 carbon atoms, having an intrinsic viscosity above 0.5 and having an iodine number less than 10, in a heat-polymerizable monomer comprising at least 90% by weight of an alkyl methacrylate ester, and then heating the resultant mixture at about 20125 C. to effect polymerization of said heat-polymerizable monomer in situ in the presence of said aromatic-olefin copolymer.

13. Product comprising a homogeneous mixture of a high molecular weight copolymer comprising about 10-60% by weight of a polymerizable mono-:olefinic aromatic compound selected from the group consisting of 12 hydrocarbons and chlorostyrenes, and about 90-40% of a mono-olefin of 2 to 8 carbon atoms, said copolymer having an intrinsic viscosity above 0.5 and having an iodine number less than 10, having homogeneously admixed With said copolymer another high molecular weight polymerization product made by heating to polymerization temperature 50-95% by weight of a heat-polymerizab le monomer comprising at least 74% by Wt. of a monoolefinic aliphatic compound, in situ in the presence of 5 10 to 50% by Weight of the first-mentioned copolymer.

References Cited in the file of this patent UNITED STATES PATENTS France Sept. 13, 1943 

5. PROCESS WHICH COMPRISES DISSOLVING ABOUT 5 TO 50% BY WEIGHT OF A COPOLYMER OF ABOUT 10-60% BY WEIGHT OF A POLYMERIZABLE MONO-OLEFIN AROMATIC COMPOUND SESELECTED FROM THE GROUP CONSISTING OF HYDROCARBONS AND CHLOROSTYRENES, AND ABOUT 90-40% OF A MONO-OLEFIN OF 2 TO 8 CARBON ATOMS, HAVING AN INTRINSIC VISCOSITY ABOVE 0.5 AND HAVING AN IODINE NUMBER LESS THAN 10, IN 50 TO 95% BY WEIGHT OF A COMPATIBLE HEAT POLYMERIAZABLE MONOMER COMPRISING AT LEAST 74% BY WEIGHT OF AN UNSATURATED ALIPHATIC COMPOUND SELECTED FROM THE GROUP CONSISTING THEN HEATING THE RESULTANT MIXTURE AT ABOUT 20* -125* C. TO EFFECT POLYMERIZATION OF SAID HEAT-POLYMERIZABLE MONOMER IN SITU IN THE PRESENCE OF SAID AROMATIC-OLEFIN COPOLYMER. 